Unimolecular dissociation reactions of methyl benzoate radical cation.
The blackbody infrared radiation induced dissociation of methyl benzoate (C8H8O2(+*)) radical cation was investigated by using a Fourier transfer ion cyclotron resonance mass spectrometer equipped with a resistively heated (wire temperatures of 400-1070 K) wire ion guide. We observed product ion branching ratios that are strongly dependent upon wire temperature. At low temperatures (670-890 K) the major product ion C7H8 (+*) (m/z 92), which is formed by loss of CO2, and at higher temperatures (above 900 K), loss of methoxy radical ((*)OCH3) competes with loss of CO2. The energies of the various reactant ions and transition states for product ion formation were estimated by using density functional theory molecular orbital calculations, and a proposed mechanism for the dissociation chemistry of C8H8O2 (+*) involving a multistep rearrangement reaction is tested using the Master Equation formalism.
Huang
Yiqun
Y
Department of Chemistry, The Laboratory for Biological Mass Spectrometry, Texas A&M University, College Station, Texas 77842, USA.
Peterman
Scott
S
Tichy
Shane E
SE
North
Simon W
SW
Russell
David H
DH
D001565:Benzoates / Q000737:chemistry*; D005583:Fourier Analysis; D006859:Hydrogen / Q000737:chemistry; D007259:Infrared Rays; D007700:Kinetics; D011789:Quantum Theory; D013696:Temperature; D013816:Thermodynamics
D001565:Benzoates; C044605:methyl benzoate; D006859:Hydrogen